CN111423879B - Multimode-excited single-red-light nano fluorescent material and preparation method thereof - Google Patents

Multimode-excited single-red-light nano fluorescent material and preparation method thereof Download PDF

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CN111423879B
CN111423879B CN202010429134.0A CN202010429134A CN111423879B CN 111423879 B CN111423879 B CN 111423879B CN 202010429134 A CN202010429134 A CN 202010429134A CN 111423879 B CN111423879 B CN 111423879B
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fluorescent material
ercl
ybcl
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CN111423879A (en
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毛艳丽
刘越峰
潘根才
张华芳
高惠平
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Henan University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention discloses a multimode excited single red light nanometerThe fluorescent material and the preparation method thereof comprise the following steps: (1) YbCl with the concentration of 0.5-2.5mmol/ml is respectively prepared3、ErCl3、MnCl2And an aqueous solution of NaF; (2) dissolving 0.3g NaOH in 2-6ml deionized water, adding 5-15ml ethanol and 5-15ml oleic acid, and stirring; (3) respectively combine YbCl3、ErCl3And MnCl2Adding the solution into the step (2), and stirring; (4) adding 1-3mmol NaF into the solution in the step (3), and stirring; (5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 140-240 ℃ for 100-400 minutes to obtain a fluorescent product; (6) and (5) cooling the fluorescent product in the step (5) to room temperature, centrifuging and washing to obtain the fluorescent material.

Description

Multimode-excited single-red-light nano fluorescent material and preparation method thereof
Technical Field
The invention belongs to the field of nano fluorescent materials, and particularly relates to a multimode-excited single-red-light nano fluorescent material and a preparation method thereof.
Background
The rare earth doped fluorescent nano material has the advantages of narrow light-emitting band, high color purity, bright color and the like, and has stable physical and chemical properties, high temperature resistance and irradiation resistance, thereby being widely applied. Increasing the concentration of the dopant in the fluorescent nanomaterial is an effective way to increase the luminous intensity thereof. And a smart nano material microstructure and a proper dopant pairing ion are constructed, so that concentration quenching can be greatly reduced, and heavy doping of a sensitizer and an activator is realized. Meanwhile, the rare earth ions have rich energy levels, and the high doping concentration increases the absorption of the energy of the exciting light, so that the luminescence in a down-conversion mode and an up-conversion mode can be effectively realized, and the effect of multi-wavelength excitation is achieved. Multimode excitation not only enables high-capacity information storage, but also enables information identification under radiation of a specific wavelength. Colorless anti-counterfeiting based on up-conversion luminescence has better concealment. High-purity single red light emission is not easy to scatter and has strong penetrating power. Therefore, the multimode-excited single red light nano material has good application prospect in the fields of fluorescence anti-counterfeiting, biological fluorescence labeling, illumination display and the like.
Disclosure of Invention
The invention provides a multimode-excited single-red-light nano fluorescent material and a preparation method thereof, aiming at the problems of single detection light source, complex preparation steps and simple fluorescent anti-counterfeiting mode of the existing fluorescent anti-counterfeiting material, so that the multimode-excited single-red-light nano fluorescent material is realized, the preparation process is simple, the repeatability is good, the cost is low, and the fluorescent anti-counterfeiting material has wide application prospect.
In order to achieve the purpose, the invention provides the following main technical scheme:
a preparation method of a multimode excited single red light nano fluorescent material comprises the following steps:
(1) YbCl with the concentration of 0.5-2.5mmol/ml is respectively prepared3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g of NaOH in 2-6ml of deionized water, adding 5-15ml of ethanol and 5-15ml of oleic acid, and stirring for 5-30 minutes;
(3) mixing YbCl3、ErCl3And MnCl2Adding the solution into the step (2), and continuously stirring for 5-30 minutes;
(4) adding 1-3mmol NaF into the solution in the step (3), stirring for 20-40 minutes, and adding NaF in a form of NaF aqueous solution;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 140-240 ℃ for 100-400 minutes to obtain a fluorescent product;
(6) and (5) cooling the fluorescent product in the step (5) to room temperature, centrifuging and washing to obtain a precipitate which is the multimode excited single red light nano fluorescent material.
Further, steps (2) to (4) are all carried out at a constant temperature of 30 to 70 ℃.
Further, step (3) (YbCl)3+ErCl3) And MnCl2In a molar ratio of 3: 2 and YbCl3And ErCl3The molar ratio of (0-2.5) to (0.5-3). Further, YbCl3The addition amount of (a) is 0-0.25 mmol, ErCl3The addition amount of (A) is 0.05 mmol-0.3 mmol, MnCl2The amount of addition of (2) was 0.2 mmol.
The single red light nanometer fluorescent material excited by multiple modes prepared by the preparation method.
The method for preparing the heavily doped multi-mode excited single-red-light nano fluorescent material with the core-shell structure by using the multi-mode excited single-red-light nano fluorescent material as the core material comprises the following steps:
(7) dispersing the multimode excited single red light nano fluorescent material in 1-2ml of cyclohexane for later use; YbCl with the concentration of 0.5-2.5mmol/ml is respectively prepared3、ErCl3、MnCl2And an aqueous solution of NaF;
(8) dissolving 0.3g of NaOH in 2-6ml of deionized water, adding 5-15ml of ethanol and 5-15ml of oleic acid, stirring for 5-30 minutes to obtain a mixture, adding all the cyclohexane solution in the step (7) into the mixture, and stirring for 5-30 minutes;
(9) 0.1-0.3mL of YbCl3、ErCl3And MnCl2Adding the solution into the step (8) in proportion, and continuously stirring for 5-30 minutes;
(10) adding 1-3mmol NaF into the solution in the step (9), stirring for 20-40 minutes, and adding NaF in a form of NaF aqueous solution;
(11) transferring the solution in the step (10) into an autoclave, and reacting at 140-240 ℃ for 100-400 minutes to obtain a product;
(12) and (4) cooling the product in the step (11) to room temperature, centrifuging, washing, and drying the obtained precipitate to obtain the final product.
Further, steps (8) to (10) are all carried out at a constant temperature of 30 to 70 ℃.
Further, YbCl in step (9)3、ErCl3And MnCl2The molar ratio of (1-2.5): 0.5-2): 2, and (YbCl)3+ErCl3) And MnCl2The molar ratio of (A) to (B) is 3: 2. Further, YbCl3The addition amount of (a) is 0.1 mmol-0.25 mmol, ErCl3The addition amount of (A) is 0.05 mmol-0.2 mmol, MnCl2The amount of addition of (2) was 0.2 mmol.
Step (3) preparation of core Material (YbCl)3+ErCl3+MnCl2) And step (9) preparation of the coating material (YbCl)3+ErCl3+MnCl2) The ratio of the number of moles of (a) to (b) is 1: 1.
Further, the drying means drying at 60 ℃ for 3 to 7 hours.
The preparation method is used for preparing the heavy doping multi-mode excited single red light nanometer fluorescent material with the core-shell structure.
The invention has the following advantages:
(1) the hollow structure and the core-shell structure reduce the concentration quenching of the heavily-doped fluorescent material and well improve the luminous intensity of the material.
(2) The invention is based on Er3+、Yb3+The heavily doped core-shell design, the high-concentration doping and the energy transfer path matched between the sensitizer and the activator effectively play the down-conversion or up-conversion luminescent mode of the rare earth ions, thereby realizing the multi-wavelength excitation of the material. The excitation peak of the material at the probe wavelength of 668nm is distinct and sharp (FIG. 3), indicating that the material can be excited by 378, 486 and 522nm light sources. Meanwhile, based on the up-conversion principle, the material can also be excited by 808 and 980nm light sources. The fluorescence spectra of FIG. 4 show that the material has a red emission in the visible region of 650-675nm under excitation at 378, 486, 522nm, 808 and 980 nm.
(3) The multimode excitation characteristic of the heavily doped material of the invention ensures that the material has wide application prospect in the field of anti-counterfeiting application. (FIG. 5)
(4) The preparation method is simple, the sample performance is stable, and the method is more beneficial to large-scale commercial production.
Drawings
FIG. 1 is a scanning electron micrograph of a final product obtained in step (11) of example 1, wherein the inset shows an enlarged view of the scanning electron micrograph;
FIG. 2 is a transmission electron micrograph of a single particle of the final product obtained in step (11) of example 1;
FIG. 3 is an excitation spectrum of the final product obtained in step (11) of example 1 at a detection wavelength of 668 nm;
FIG. 4 shows photoluminescence spectra of the product obtained in step (6) and the final product obtained in step (11) in example 1 under excitation at (a) 379nm, (b) 486nm, (c) 522nm, (d) 808nm and (e) 980nm, respectively; the black line represents the product obtained in the step (6), and the red line represents the final product obtained in the step (11);
FIG. 5 is a digital photograph of the artistic model doped with fluorescent material obtained in example 1 under irradiation of light of different wavelengths: (a) under a common light source; (b) 379 nm; (c) - (d) 486 nm; (e) - (f) 522 nm; (g) 980 nm; (h) 808 nm. Wherein (c) and (e) are photographs of the model under 486nm and 522nm wavelength illumination, respectively, and (d) and (f) are photographs after 600-700nm bandpass filters were added in front of the camera.
Detailed Description
The following examples are presented to illustrate the present invention and to enable those skilled in the art to better understand and practice the invention. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended.
Example 1
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 5ml deionized water, adding 10ml ethanol and 10ml oleic acid, and stirring for 10 minutes;
(3) respectively adding 0.2ml of YbCl3、0.1ml ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 3mL of NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure autoclave, reacting at 190 ℃ for 160 minutes to obtain fluorescent products capable of being excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980nm, wherein the specific result is shown in figure 4;
(6) after the product in the step (5) is cooled to room temperature, repeatedly centrifugally cleaning the product for 3 to 6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 2ml of cyclohexane for later use;
(7) dissolving 0.3g of NaOH in 5ml of deionized water, adding 10ml of ethanol and 10ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.2ml of YbCl3、0.1ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 2mL of NaF solution into the solution in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4) and (7) - (9) are carried out in a constant temperature environment of 60 ℃;
(10) transferring the solution in the step (9) into an autoclave, and reacting at 190 ℃ for 160 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven at 60 ℃ for 7 hours to obtain the final product. FIG. 1 is a scanning electron micrograph of the heavily doped material obtained in example 1, FIG. 2 is a transmission electron micrograph of the heavily doped material, and FIG. 1 shows that the sample is a sandwich pie structure of about 500 nm. And figure 2 shows that the sandwich cake-like particle is a hollow core-shell structure.
The excitation peak of the material at the probe wavelength of 668nm is distinct and sharp (FIG. 3), indicating that the material can be excited by 378, 486 and 522nm light sources. Meanwhile, based on the up-conversion principle, the material can also be excited by 808 and 980nm light sources. The fluorescence spectra of FIG. 4 show that the material has a red emission in the visible region of 650-675nm under excitation at 378, 486, 522nm, 808 and 980 nm.
(12) 3g of polymethyl methacrylate (PMMA) was dissolved in 5mL of chloroform with sonication, and then 1mL of a cyclohexane solution containing 0.25mmol of fluorescent particles having a core-shell structure was added thereto, and the mixture solution was mixed with sonication sufficiently and then poured into a mold. The mixed solution was dried at room temperature for 20 hours to evaporate the solvent, to prepare an art model.
FIG. 5 is a digital photograph of the artistic model doped with fluorescent material obtained in example 1 under irradiation of light of different wavelengths, wherein (a) the model is colorless and transparent and does not emit light under a common light source; panel (b) shows the material glowing red at 379 nm; graphs (c) and (e) are photographs of the model under 486nm and 522nm wavelength illumination, respectively, because the 486nm and 522nm excitation lights are themselves very bright, masking the red light emitted by the material. (d) And (f) are photographs taken after a 600-700nm bandpass filter was added in front of the camera, and the graphs (d) and (f) show red light emitted from the material itself, demonstrating that the material emits red light first at 486nm and 522nm excitation wavelengths, and graphs (g) and (h) show that the material emits red light at 980nm and 808nm excitation wavelengths.
Example 2
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 3ml deionized water, adding 15ml ethanol and 10ml oleic acid, and stirring for 10 minutes;
(3) respectively adding 0.1ml of YbCl3、0.2ml ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 3ml of NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 200 ℃ for 100 minutes to obtain fluorescent products which can be excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980 nm;
(6) and (5) cooling the product in the step (5) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 2ml of cyclohexane for later use.
(7) Dissolving 0.3g of NaOH in 2ml of deionized water, adding 8ml of ethanol and 15ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.1ml of YbCl3、0.2ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 3mL of NaF solution into the solution obtained in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4), (7) - (9) are carried out in a constant temperature environment of 40 ℃.
(10) Transferring the solution in the step (9) into an autoclave, and reacting at 200 ℃ for 120 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven at 60 ℃ for 7 hours to obtain the final product.
Example 3
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 4ml deionized water, adding 12ml ethanol and 12ml oleic acid, and stirring for 10 minutes;
(3) 0.1ml of YbCl3、0.2ml ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 2ml of the NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 220 ℃ for 100 minutes to obtain fluorescent products which can be excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980 nm;
(6) after the product in the step (5) is cooled to room temperature, repeatedly centrifugally cleaning the product for 3 to 6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 2ml of cyclohexane for later use;
(7) dissolving 0.3g of NaOH in 4ml of deionized water, adding 12ml of ethanol and 12ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.2ml of YbCl3、0.1ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 2mL of NaF solution into the solution in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4) and (7) - (9) are carried out in a constant temperature environment of 40 ℃.
(10) Transferring the solution in the step (9) into an autoclave, and reacting at 220 ℃ for 100 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven for 5 hours at the temperature of 60 ℃ to obtain the final product.
Example 4
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 3ml deionized water, adding 7ml ethanol and 16ml oleic acid, and stirring for 10 minutes;
(3) 0.3ml of ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 3ml of NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 170 ℃ for 200 minutes to obtain fluorescent products which can be excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980 nm;
(6) and (5) cooling the product in the step (5) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 1ml of cyclohexane for later use.
(7) Dissolving 0.3g of NaOH in 3ml of deionized water, adding 7ml of ethanol and 16ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.2ml of YbCl3、0.1ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 3ml of NaF solution into the solution in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4) and (7) - (9) are carried out in a constant temperature environment of 30-70 ℃.
(10) Transferring the solution in the step (9) into an autoclave, and reacting at 170 ℃ for 200 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven at 60 ℃ for 7 hours to obtain the final product.
Example 5
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 5ml deionized water, adding 10ml ethanol and 10ml oleic acid, and stirring for 10 minutes;
(3) 0.25ml of YbCl3、0.05ml ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 3ml of NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 200 ℃ for 140 minutes to obtain fluorescent products capable of being excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980 nm;
(6) and (5) cooling the product in the step (5) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 1ml of cyclohexane for later use.
(7) Dissolving 0.3g of NaOH in 5ml of deionized water, adding 10ml of ethanol and 10ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.25ml of YbCl3、0.05ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 3mL of NaF solution into the solution obtained in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4) and (7) - (9) are carried out in a constant temperature environment of 50 ℃.
(10) Transferring the solution in the step (9) into an autoclave, and reacting at 200 ℃ for 140 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven for 3 hours at the temperature of 60 ℃ to obtain the final product.
Example 6
A preparation method of a heavy doping multimode excited single red light nanometer fluorescent material with a core-shell structure comprises the following steps:
(1) YbCl with the concentration of 1mmol/ml is prepared respectively3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g NaOH in 3ml deionized water, adding 8ml ethanol and 15ml oleic acid, and stirring for 10 minutes;
(3) 0.1ml of YbCl3、0.2ml ErCl3And 0.2ml MnCl2Adding the solution into the step (2), and continuing stirring for 10 minutes;
(4) adding 2mL of NaF solution into the solution in the step (3), and stirring for 30 minutes;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 210 ℃ for 120 minutes to obtain fluorescent products capable of being excited by wavelengths of 379nm, 486nm, 522nm, 808nm and 980 nm;
(6) and (5) cooling the product in the step (5) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and dispersing the washed precipitate in 2ml of cyclohexane for later use.
(7) Dissolving 0.3g of NaOH in 3ml of deionized water, adding 8ml of ethanol and 15ml of oleic acid, stirring for 10 minutes, adding all the cyclohexane solution in the step (6) into the reactant, and continuing stirring for 10 minutes;
(8) 0.25ml of YbCl3、0.05ml ErCl3And 0.2ml MnCl2Adding the solution into the step (7), and continuing stirring for 10 minutes;
(9) adding 2ml of the NaF solution into the solution in the step (8), and stirring for 30 minutes;
wherein, the steps (2) - (4), (7) - (9) are carried out in a constant temperature environment of 50 ℃.
(10) Transferring the solution in the step (9) into an autoclave, and reacting at 210 ℃ for 120 minutes to obtain a product;
(11) and (3) cooling the product in the step (10) to room temperature, repeatedly centrifuging and cleaning the product for 3-6 times by using cyclohexane and absolute ethyl alcohol, and drying the washed precipitate in a drying oven for 5 hours at the temperature of 60 ℃ to obtain the final product.

Claims (7)

1. A preparation method of a heavily doped multimode excited single red light nanometer fluorescent material with a core-shell structure is characterized by comprising the following steps:
(1) dispersing the multimode excited single red light nano fluorescent material in 1-2ml of cyclohexane for later use; YbCl with the concentration of 0.5-2.5mmol/ml is respectively prepared3、ErCl3、MnCl2And an aqueous solution of NaF;
(2) dissolving 0.3g of NaOH in 2-6ml of deionized water, adding 5-15ml of ethanol and 5-15ml of oleic acid, stirring for 5-30 minutes to obtain a mixture, adding all the cyclohexane solution in the step (1) into the mixture, and stirring for 5-30 minutes;
(3) respectively adding 0.1-0.3ml of YbCl3、ErCl3And MnCl2Adding the solution into the step (2), and continuously stirring for 5-30 minutes;
(4) adding 1-3mmol NaF into the solution in the step (3), stirring for 20-40 minutes, and adding NaF in a form of NaF aqueous solution;
(5) transferring the solution in the step (4) into a high-pressure kettle, and reacting at 140-240 ℃ for 100-400 minutes to obtain a product;
(6) cooling the product in the step (5) to room temperature, centrifuging, washing, and drying the obtained precipitate to obtain a final product;
the multimode excited single red light nanometer fluorescent material is obtained by the following processes:
(a) YbCl with the concentration of 0.5-2.5mmol/ml is respectively prepared3、ErCl3、MnCl2And an aqueous solution of NaF;
(b) dissolving 0.3g of NaOH in 2-6ml of deionized water, adding 5-15ml of ethanol and 5-15ml of oleic acid, and stirring for 5-30 minutes;
(c) mixing YbCl3、ErCl3And MnCl2Adding the solution into the step (b), and continuously stirring for 5-30 minutes;
(d) adding 1-3mmol NaF into the solution in the step (c), stirring for 20-40 minutes, and adding NaF in the form of NaF aqueous solution;
(e) transferring the solution in the step (d) into an autoclave, and reacting at 140-240 ℃ for 100-400 minutes to obtain a fluorescent product;
(f) and (e) cooling the fluorescent product in the step (e) to room temperature, centrifuging and washing to obtain a precipitate which is a multimode excited single red light nano fluorescent material.
2. The method for preparing a heavily doped multimode-excited single-red-light nano fluorescent material with a core-shell structure according to claim 1, wherein the steps (b) - (d) are performed at a constant temperature of 30-70 ℃.
3. The method for preparing a heavily doped multimode-excited single-red-light nano fluorescent material with a core-shell structure according to claim 1, wherein in the step (c) (YbCl)3+ErCl3) And MnCl2In a molar ratio of 3: 2 and YbCl3And ErCl3The molar ratio of (0-2.5) to (0.5-3).
4. The preparation method of the heavily doped multimode-excited single-red-light nano fluorescent material with the core-shell structure according to claim 1, wherein the steps (2) - (4) are all performed at a constant temperature of 30-70 ℃.
5. The method for preparing a single red light nanometer fluorescent material excited by heavily doped multiple modes of the core-shell structure according to claim 1, wherein YbCl is adopted in the step (3)3、ErCl3And MnCl2The molar ratio of (1-2.5): 0.5-2): 2, and (YbCl)3+ErCl3) And MnCl2The molar ratio of (A) to (B) is 3: 2.
6. The method for preparing the heavily doped multimode-excited single-red-light nano fluorescent material with the core-shell structure according to claim 1, wherein the drying is performed at 60 ℃ for 3-7 hours.
7. The heavily doped multi-mode excited single red light nano fluorescent material with the core-shell structure prepared by the preparation method of any one of claims 1 to 6.
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